Sulfonyl compounds

ABSTRACT

Compounds of the formula

United States Patent 1191 Piesch et al.

[451 May 6,1975

[ SULFONYL COMPOUNDS 21 Appl. No.2 259,201

Primary Examiner-Donald G. Daus Assistant ExaminerRaymond V. Rush Attorney, Agent, or Firm-Connolly and Hutz [57] ABSTRACT Compounds of the formula R SO X wherein X is 9 Z ,Z JHMZZZ" 3141 N-1'i 411-11" \N-CILSQO-ES I i C p \C 4 r R R n B u R -CH--:111-cco ib-0OC I2l-Cll-S0 -R, --CH--SI1 l i I R R Y 2 R-SO, CH--SR A '1) -CIl IH f R3 or 016112-20- I 1 5 Y' Y I l 9 12-50,, -c;: an-cor n-s0 -c11-1:1z-so. ,.2'

[30] Foreign Application Priority Data R and R5 are aryl, aralkyl, heteroaryl, cycloalkyl or al- June 5, 1971 Germany 2123011 y and are hydrogen, carbflxy 0r carboxylate; R is aryl, aralkyl, cycloalkyl or alkyl; R" is R2 or 52 us. (:1 260/251 R; 252/426; 252/428; s Y is alkylene. Cycloalkylene or Phenylene,

260/29.6 MQ; 260/29.6 HN; 260/239 BF,

260/244 R; 260/256.5 R; 260/247.l M;

260/556 A; 260/556 B; 260/556 S; 260/558 S; 260/559 T; 260/562 R; 260/562 P;

[51] Int. Cl C07d 51/18 [58] Field of Search 260/251 R, 309.7, 256.5 R, 260/247.1 M, 293.69, 293.7

[56] References Cited UNITED STATES PATENTS 3,549,638 12/1970 Tesoro et al .1 260/268 Y is Y or a direct bond and Z is alkylene, hydroxy substituted alkylene, alkylene interrupted by a hetero atom or and methods of preparing the same.

5 Claims, No Drawings SULFONYL COMPOUNDS The present invention relates to sulfonyl compounds of the formula wherein X is R and R are phenyl, naphthyl, benzyl, phenethyl, thienyl, pyrrolyl, carbazolyl, pyridyl, phenothiazinyl, cycloalkyl having 4 to 8 carbon atoms, alkyl having I to 8 carbon atoms or one of said moieties substituted by alkyl, alkoxy, alkanoyl, alkanoyloxy or alkanoylamino having 1 to 4 carbon atoms or dialkylamino having 1 to 4 carbon atoms in each alkyl group, hydroxy, cyano, chlorine, fluorine, bromine, nitro, trifluoromethyl or carboxy;

R and R are R, hydrogen, carboxy or carboxylate;

R is phenyl, naphthyl, benzyl, phenethyl, cycloalkyl having 4 to 8 carbon atoms, alkyl having 1 to 8 carbon atoms or one of said moieties substituted by alkyl, alkoxy, alkanoyl, alkanoyloxy or alkanoylamino having I to 4 carbon atoms or dialkylamino having 1 to 4 carbon atoms in each alkyl group, hydroxy, cyano, chlorine, fluorine, bromine, nitro, trifluoromethyl or carboxy;

R is R or hydrogen;

Y is alkylene having I to 8 carbon atoms, cycloalkylene having 4 to 8 carbon atoms or phenylene;

Y is Y or a direct bond and Z is alkylene having 2 to 3 carbon atoms, hydroxy substituted ethylene, -CH C-CH or CH CH- l l HN NH c pared in accordance with three different methods. These three methods are initially explained for the preparation of compounds of the formulae Ia and lb as follows:

METHOD A In this method, a sulfinic acid of the formula ll or a salt of a sulfinic acid, preferably the sodium or potassium salt, is reacted with an aldehyde of the formula III in a suitable solvent to an oxysulfonyl compound of the formula IV:

(1) n-som CHO R-SO -lCHOH h l R1 1 II III IV The oxysulfonyl compound of the formula IV is then, if required after its isolation, reacted with a compound of formula Va or Vb to obtain respectively la or lb:

(2a) R-os -ciion HSR2- R-so -cn-sR IV Va Ia '11) Z 3 li-SO -CHOK +HN N-R R-SO2 z i 3 c -CHN /N-R H IV v1 Ib O The oxysulfonyl compound of the formula IV is, as a rule, not particularly thermally stable so that it is generally advisable not to exceed a reaction temperature of 50C.

METHOD B A sulfinic acid of the formula ll, an aldehyde of the formula III and a compound of the formula Va or Vb are simultaneously reacted in a suitable solvent:

METHOD C In this method, a compound of the formula Va or Vb is first reacted with an aldehyde of the formula III to obtain a compound of the formula Vla or Vlb:

(3a) a-so tt QCH Hsr" f R-SO CHSH l l R R I 1 III Vs Ia Z Z 3 3 (3b) R-SO3H OCH HN N-R R-SOQ-CH-N NJ?- H c R ll ll 9 0 II III 'b Ib J 2 (Ha) OCH HSn" amen-3R III Va VIa i Z 3 3 ib) OCH PIN N-a HO-CH-N N-R l 1 L R C R- 6 III Vb VIb As solvents, there are preferably used glacial acetic This reaction is also carried out in a suitable solvent acid, formic acid, alkanols having 1 to 4 carbon atoms, or solvent mixture. Suitable solvents include water, glawater, dimethylformamide, dimethylsulfoxide or 501- cial acetic acid, formic acid, ethylene chloride, dimethvent mixtures, particularly mixtures of the stated solylformamide, dimethylsulfoxide, alkanols having l to 4 vents. Normally, the three components are stirred in carbon atoms and mixtures thereof. the solvent employed at temperatures between 5 and Rather drastic reaction requirements such as temper- 100C. The sulfinic acid may also be used in the form atures of up to l50C and above, may be selected so of a salt, e.g. its potassium or sodium salt. After some 60 that even compounds which are difficult to dissolve time, the novel compounds precipitate in the form of and/or slow to react of the formulae Va and Vb may be crystals. Upon their isolation, they may be recrystalreacted. lizcd from a suitable solvent. Finally, the compound of the formula Vla or Vlb, if This process generally gives good yields. But in some 5 required after its isolation, is reacted with a sulfinic instances, it proceeds unsatisfactorily, particularly when the reaction between the compound of the foracid of the formula II in a suitable solvent under mild reaction conditions:

VIa

n-sogr II VIb Ib Solvents in this reaction include, for example, water, alkanols having 1 to 4 carbon atoms, formic acid, glacial acetic acid, dimethylfonnamide, dimethylsulfoxide and mixtures thereof.

The reaction temperatures for the reaction of the compounds Vla or Vlb with the sulfinic acids are normally between 0 and 80C.

Even with Method C, the sulfinic acid ll may be used in the form of a salt. Moreover, in certain instances the aldehyde group may also be acetalized.

The novel compounds to lg may also be prepared according to the illustrated methods A, B and C. If, for example, with the three methods A, B or C, a com pound wherein R is H is used as a compound of the formula Vb, i.e., the compound V0:

R-SO -CIl-N a 5 N-CH-SO2-H formulae then one obtains as a final product a compound of the l 1 i 1 structure R i R 1 I 1 it PM) (Hi ll\ it it an 1 C H h L! O R-soq-czr-n i\ Cl?-SO R I I h 1 4 This compound may in turn be used with Methods A, B or C instead of compound Vb and yields, depending on the choice of aldehyde and sulfinic acid components, compounds of the formula:

may also be repared.

Symmetrical compounds of the formula I i may also be prepared according to Methods A and B when the reactions are carried out in the molar ratio of 2:1 and 2:2:] respectively. The reaction equation of Method A then reads:

The reaction equation of Method B then reads:

3c) 2 R-30,,H aocn m1 Mi 1 n c N 0 II III 'v'u R-s0 -CHN N-cH-so, -R

1 C R ll 0 45 if m the reaction equations 26 and 3c, the compound Va is replaced by a compound of the formula Vd:

H,NCOOYOOCNH and if the remaining procedure is exactly the same as with Methods A and B, then compounds of the general formula 1 d are obtained.

If formaldehyde is used as aldehyde III with Methods A, B or C, then compounds are obtained wherein R H. Preferred novel compounds are those wherein R COOH. These are obtained when glyoxylic acid (OCH- 5 COOH) is used as aldehyde ill with Methods A, B or Novel compounds of the formulae Ie, Ifand Ig are obtained when a dialdehyde Ilia is used as an aldehyde component with Methods A, B and C and if the molar ratios are changed accordingly. Method A then proceeds as follows:

Ve Im Q then stands for the residues -NHCOR -NH- 80 R and SR*. The reaction equation for Method B then reads:

35:) 2 iZ-SOgii OCH 2 HQ R-S0 ?H-Q l Y1 9' 1 l OCH RSO; '-CH-Q II IIIa Ve I m Method C, with the use of dialdehydes, proceeds as follows:

The statements made with respect to reaction conditions and solvents in Methods A. B and C also hold true for their modifications.

Examples of sulfinic acids of the formula 11 include methane-, ethane-, propane-, butane-, benzene-, ptoluene-, p-chlorobenzene-, 4-methoxybenzene-, 3-trifluoromethylbenzene-, 4nitrobenzene-, 3- cyanobenzene-, 4-acetaminobenzene-, 3,4-dichloro-, 2,5-dichloroor 2,6-dichlorobenzene-, 2,3,4-trichlorobenzene-, 2,5-dimethoxybenzene-, 3,4,5-trimethoxybenzene-, 2-methoxy-5-chlorobenzene-, 2-chloro-5- nitrobenzene-, 2-chloro-S-trifluoromethylbenzene-, 2-chloro--methylbenzene-, 4-hydroxy-5-carboxybenzene-, Z-thiophene-and Z-naphthalene-sulfinic acid.

As previously indicated, salts of the sulfinic acid, es pecially the sodium and potassium salts, may be used.

Sulfinic acids may, for example, be obtained either by reduction of the corresponding sulfonic acid chlorides (these again are obtainable by the reaction of the corresponding substituted benzenes with chlorosulfonic acid or from the corresponding substituted anilines by a modified Sandmeyer reaction according to Meerwein Chem. Ber. 90, 841 (1957)) or by direct Sandmeyer reaction to the sulfinic acid. For example, the yet unknown 2-chloro-6-methylbenzene sulfinic acid (melting point: 110C. with decomposition) was prepared from 2-chloro-6-methylaniline by way of 2-chloro-6-methylbenzene sulfochloride (boiling point of 1 17C. at 1.3mm). The preparation of sulfinic acids is summarized in Houben-Weyl, Methoden der Organischen Chemie, Vol. 9 (19), pp. 299 et. seq.

As aldehydes of the formula ll], the following may be used, for example:

formaldehyde acetaldehyde propionaldehyde nor i-butyric aldehye nor i-valeric aldehyde caproic aldehyde benzaldehyde chloral bromal p-chlorobenzaldehyde o-chlorobenzaldehyde p-bromobenzaldehyde p-methoxybenzaldehyde o-methoxybenzaldehyde 3,4,5-trimethoxybenzaldehyde o-hydroxybenzaldehyde 2,5-dichlorobenzaldehyde 3,4-dichlorobenzaldehyde p-dimethylaminobenzaldehyde p-acetylaminobenzaldehyde tolylaldehyde m-nitrobenzaldehyde p-nitrobenzaldehyde furfuraldehyde furfural acrolein crotonaldehyde pyridyl-3-aldehyde glyoxylic acid (also in the form of its salts, particularly its sodium, potassium, calcium, ammonium, triethanolammonium and triethylammonium salt).

As dialdehydes of the formula Ila, the following may be used, for example:

glyoxal malondialdehyde succinic dialdehyde o-plithalaldehyde isophthalaldehyde terephthalaldehyde.

As thiols (mercaptans) of the formula Va, the following may be used, for example:

methane thiol ethane thiol propane thiol butane thiol B-hydroxyethane thiol benzene thiol p-chlorobenzene thiol p-hydroxybenzene thiol 3,4-dichlorobenzene thiol 2-chloro-5-trifluoromethylbenzene thiol 3-trifluoromethylbenzene thiol 4-acetylaminobenzene thiol 4-dimethylaminobenzene thiol 2,3,4-trichlorobenzene thiol 4-bromobenzene thiol 2,5-dimethoxybenzene thiol 5-chloro-2-methoxybenzene thiol l-naphthalene thiol Z-naphthalene thiol 2-chloro-6-methylbenzene thiol 4-methylbenzene thiol phenylmethane thiol 3,4-dimethylbenzene thiol cyclopentane thiol p-mercaptobenzoic acid mercapto acetic acid mercapto acetic acid methylester mercapto acetic acid ethylester mercapto acetic acid propylester.

Thiols may be prepared in accordance with known per se processes, e.g., by alkylation or arylation of hydrogen sulfide and by the conversion of other sulfuric functions into the SH group. In the alkylation of hydrogen sulfide, it is known to replace, for the sake of expedience, the second H atom by residues which may be easily removed again. For example, sodium thiosulfate, thiourea or xanthogenates are alkylated and the alkylation products converted into thiols by acidification or hydrolysis.

Aromatic thiols are advantageously prepared by the reduction of sulfonic acid chlorides.

Starting compounds of the formula Vb or Vc are cyclic urea or cyclic urea derivatives. There may be used,

for example:

l l an HN NH 1 HO OH RN Er \Jj" a a RN CH HN NH (ethylene urea) (propylene urea) (butylene urea) (acetylene urea) HN N-C H 3 HM N-C2H5 an N-CqH The noncrcasing finishing agents in the trade are various methylolated cyclic ureas under the trade names Cassurit Rl, Cassurit LR or Cassurit BFR. for example. Their structures, for example, are as follows:

HO OH HocH -x u-ca cii; HOCHQ-NYN-CHEOH; O 0

l5 ROCHE-N N-CHH Such methylolated cyclic ureas may be directly reacted 20 with a sulfinic acid according to Method C instead of the compounds Vla or Vlb, e.g.:

Starting compounds of the formula W1 may, for example, be obtained easily from urea and a diol Vll according to the methods known for the preparation of urethanes:

VII

(Ta) HO-Y-OH 2 Cl-CO-Cl VIIa Cl-COO-Y-OOC-Cl VIII (7b) Cl-COO-Y-OOC-Cl 2 m VlII n n-coa-y-oocmn For the preparation of compounds of the formula If, carbonamides H NCOR are needed as starting compounds. Suitable carbonamides, for example, are:

formamide acetamide propionamide butyramide trichloroacetamide benzamide p-tolylamide p-trifluoromethylbenzamide p-cyanobenzamide o-chlorophenoxyacetamide p-methoxyphenoxyacetamide phenoxyacetamide 2,5-dimethylphenoxyacetamide.

Carbonamides may be prepared easily, for example, by the reaction of the corresponding carbonic acid esters or acid chlorides with ammonia.

For the preparation of compounds of the formula lg, sulfonamides, H NSO R are needed as starting compounds. Suitable sulfonamides, for example, are:

methane sulfonamide ethane sulfonamide propane sulfonamide butane sulfonamide benzene sulfonamide 4-carboxybenzene sulfonamide 3-trifluoromethylbenzene sulfonamide 2,4-dimethoxybenzene sulfonamide 4-acetylaminobenzene sulfonamide 2,3,4-trichlorobenzene sulfonamide 3-cyanobenzene sulfonamide.

So long as the novel compounds of the Formula 1 contain a carboxyl group, they can form salts with inorganic or organic bases. Of the inorganic salts, those with cations of the first or second main group of the Periodic Table are preferred. Ammonium, sodium, potassium, calcium and copper salts are particularly preferred. Of the salts with organic cations, those derived from trimethylamine, triethylamine, triethanolarnine, morpholine, piperidine, pyrrolidine and aniline are preferred.

From the compounds containing carboxyl groups of the general formula I, the salts may be prepared in a manner known per se by reaction with inorganic or organic bases. In the preparation of alkali and earth alkali salts, particularly of the potassium, sodium and calcium salts, an alcoholate dissolved in alcohol is suitably used.

The compounds of formula I are particularly well suitable as reducing component in Redox-catalyst systems used for the production of homo and copolymers of olifinic compounds.

Oxidizing components of the Redox-catalyst system include, as customary, air and organic as well as mineral peroxy compounds, such as benzoylperoxide, ten.- butylhydroperoxide, di-tertiary-butyl peroxide, lauroyl peroxide, cumol hydroperoxide, acetyl peroxide, methylethylketone peroxide, hydrogen peroxide, potassium peroxide disulfate and ammonium peroxide disulfate.

Suitable monomers which may be polymerized with Redox-catalysts containing as reducing components compounds of the present invention are, for instance: acrylic acid, methacrylic acid as well as the salts thereof, esters and amides, methylolacrylamide or methacrylamide and their reaction products with amines and alcohols, vinylpyrrolidone, vinylcarbazole,

vinylmethyl ketone, acrylonitrile, vinylidene cyanide, esters of unsaturated alcohols, such as vinylacetate and dialkylphthalate. For the preparation of copolymers with the monomers already known there may also be used styrene, a-methyl-styrene, vinyltoluene, halogeno-styrenes, for example, 2,5-dichloro-styrene and allylbenzene.

The polymerization can be effected as precipitation, emulsion, solution and bulk polymerization.

Particularly favorable results are achieved in the case of the homo and copolymers of the acrylamide in an aqueous solution. In this respect, specially those instant compounds are valuable as components for the Redoxcatalysts system which contain a carboxyl group and, hence, dissolve in aqueous solutions or solutions of weak alkalies, such as bicarbonate or sodium carbonate solution.

The polymerization is performed in a manner known per se under atmospheric pressure and at temperatures ranging between 0-120C., preferably between 20-70C. The concentration of the instant compound which acts as reducing component of the Redoxcatalyst system is normally appr. 0.02 to 1.5 per cent by weight, related to the weight of the monomer or mixture of monomers to be polymerized. The concentration of the oxidizing component of the Redoxcatalyst system is normally between about 0.25 and 2.0 per cent by weight, likewise related to the weight of the monomer or the mixture of monomers to be polymerized.

The homopolymers manufactured by using the named Redox-catalyst systems, which contain as reducing component a compound of the present invention, distinguish themselves by a better water-solubility and a more even distribution of the molecular weight than by using known Redox-catalyst systems.

As compared to the known Redox-catalyst systems, the use of the Redox-catalyst systems, which contain as reducing component a compound of the present invention, additionally results in a substantially better and more even course of polymerization because in the event of more favorable monomer conversions the polymerization runs at lower temperatures.

In the following examples, (Z)" means with decomposition. Additionally, when is used in the tabulation in connection with the definition of Y, this has reference to a direct bond.

EXAMPLE 1 (Method A) The sodium salt of p-toluenesulfinic acid (35 g), 200 ml. water, 30 ml formic acid and 20 ml 39% formaldehyde are stirred in water for 3 hours at 40C. Then 16 g ethylene urea are added to the clear solution and it is stirred for an additional 10 minutes at 40C. and for another 2 hours at 10C. About 10 minutes after the addition of ethylene urea, the product begins to crystallize into colorless needles.

There are obtained 38.5 g (76% of the theoretical) of the compound:

having a melting point of l58C. (Z).

EXAMPLE 2 (Method B) SO -CH-NYNH having a melting point of 161C.

EXAMPLE 3 (Method C) Propylene urea (10 g), 40 g glyoxylic acid (40% aqueous), 20 ml water and 10 ml 85% formic acid are stirred for 3 hours at 8085C. This is then cooled to 40C. and a solution of 40 g of the sodium salt of ptoluene sulfinic acid in 150 ml water and 50 ml 85% formic acid is added at once. This is stirred for hours at 40C. and then 15 ml 25% hydrochloric acid is added. it is cooled to C. After standing overnight, the product is crystallized out. It is drawn off and washed with 100 ml ice water. The product may be recrystallized from isopropanol.

Yield: 30 g (58% of the theoretical) of the compound:

(ll-L $\I/ I l l 3 1 Y C r 5 It readily dissolves in aqueous sodium hydrogen carbonate solution.

EXAMPLE 4 (Method C) The sodium salt of 3,4-dichlorobenzene sulfinic acid g), 50 ml water, 50 ml 85% formic acid and 15 g Cassurit R] (dihydroxymethylethylene urea, 50% in water) are stirred for 3 hours at 50C. Crystallization begins after 20 minutes. Upon cooling to 10C. and standing overnight, the colorless needles of the com- 25 pound:

having a melting point of 210C. (Z) are drawn off and washed well with water. Recrystallization may be from dioxane. Yield: 22.6 g (87% of the theoretical).

The following compounds are prepared analogously:

. 2 R-S0 -CH-Sn 2 Melting 3 i 3 Point *0 Method -CH2CH20H 102 0 T\ m j -ocn -CIl CH OH 102 A, c

Continued I Y1 1 2 R S II 512 1 2 Melting 3 Y i 2 Point -c Method Q c1 200 (2) B, c

2S EXAMPLE 5 having a melting point of 158C. (Z). dissolved in 5 ml Into a glass polymerization vessel equipped with stirrer, thermometer, reflux cooler and dropping funnel is placed a mixture of 90 g n-butanol, 30 g butylacrylate, g ethylacrylate, g styrene, 12 g acrylic acid and 10 g hydroxypropylmethacrylate. While stirring, there are added 2 g of a compound of the formula tion obtained contains 49.5% polymer and has a viscosity of 4600 centipoise.

EXAMPLE 6 Acrylamide (250 g) is dissolved in a mixture of 750 ml water (deionized) and 0.85 g 50% NaOH. While introducing nitrogen to this solution, there are added 0.5 g dibutylamine hydrochloride, 0.25 ml of a copper acetylacetonate solution l g solution corresponds to 12.3 7 Cu), 0.25 g of the compound dimethylsulfoxide and 0.25 g ammonium peroxy disulfate.

The catalyzed reaction mixture, which is adjusted to a temperature of 20C., is transferred to a container of polyethylene. After about 1% hours, polymerization begins and the temperature of the polymerization mixture rises to 92C.

There is obtained a non-flowable, polymeric gel which, after being reduced to small pieces, and, if necessary, after being dried and milled, is completely dissolved in water. The resulting highly viscous polymer solution is excellently suitable as a flocculating agent.

EXAMPLE 7 A polyester is prepared in the following way:

30 g 1.2 propylene glycol 23 g. maleic acid anhydride 1? g phthalic acid anhydride are condensed at a temperature of l80-190C. for 8 hours in the presence of a trace of hydroquinone. Then the whole is cooled to C. and 30 g. methylmethacrylate are introduced while stirring. After further colling down to room temperature, the said polyester is obtained having an acid number of 18 and an 0H number of 20. Of this polyester there are introduced 15 g. into a beaker and 0.5 g. of the catalyst 01 @40 CII2-N\?/N-CIX2 SOB-G01 dissolved in L3 ml dimethylformamide, and as an accelerator solution, 0.5 ml commercial octa-soligencobalt-6-solution with 6% cobalt are stirred in. Subsequently a 2.0 mm thick layer is applied onto a glass plate. The layer thus obtained is completely polymerized in about 1% hours and is non-tacky.

in comparison thereto, polymerization with benzoylperoxide and octa-soligen-cobalt--solution requires about 5 days to yield a non-tacky surface.

EXAMPLE 8 T) n o S 3 YN-CH-SO Q CO H The temperature of the mixture is then brought to 50C. Then a 0.5% aqueous solution of K S O is added dropwise. As soon as the reaction is started (about minutes) and the temperature has risen to about 55-58C. in the reaction mixture, further acrylonitrile is allowed to flow in from the storage vessel in such a manner that the reaction temperature is maintained between 57 and 60C. In this manner, in the course of about 1% hours, 150 ml potassium peroxy disulfate solution and 100 ml acrylonitrile are supplied. Upon completing polymerization, stirring is continued for another hour at 65C.

The polymer obtained is filtered off and dried. It has a K-value of 86.7 measured in dimethylformamide.

We claim:

I. A compound of the formula wherein X is Z Z 3 -CH-N N-R or -C11-N N-CH-SO -R I 1 c R R II I R and R are phenyl or p-methylphenyl, 4

methoxyphenyl, p-chlorophenyl, 3-trifluoromethylphenyl, 4-nitropheny1, 3-cyanophenyl, 4- acetaminophenyl, 3,4-dichlorophenyl, 2,5- dichlorophenyl, 2,6-dichlorophenyl, 2, 3 ,4- trichlorophenyl, 2,5-dimethoxyphenyl, 3,4,5-

trimethoxyphenyl, Z-methoxy-S-chlorophenyl, 2- chloro-S-nitrophenyl, 2-chloro-5-trifluoromethylphenyl, 2-chloro-6-methylphenyl, 2-chloro-5- methoxyphenyl; R and R are phenyl, p-chlorophenyl, o-

chlorophenyl, p-bromophenyl, p-methoxyphenyl, 3,4,5-trimethoxyphenyl, o-hydroxyphenyl, 2,5- dichlorophenyl, 3,4-dichlorophenyl, pdimethylaminophenyl, p-acetaminophenyl, methylphenyl, m-nitrophenyl, p-nitropheriyl, hydrogen, carboxy or COOX wherein X, is ammonium, so-

dium, potassium, calcium, copper, trimethylammonium, triethylammonium, triethanolammonium, morpholinium, piperidinium, pyrrolidinium or anilinium;

R is hydrogen and Z is alkylene having 2 to 3 carbon atoms or hydroxy substituted ethylene.

2. The compound of claim 1 wherein Z 3 X is -CH-N N-R ll R C R is p-methylphenyl;

R is hydrogen and 3. The compound of claim 1 wherein R is 3,4-dichlorophenyl;

R is 2-chlorophenyl;

4. The compound of claim 1 wherein N- CH-S02-R5 R is p-methylphenyl;

R is p-methylphenyl;

R is carboxy;

R is carboxy and 5. The compound of claim 1 wherein z 15 x is -CH-N u-eii R R1 c R and R and R are identical and R and R are identical. 

1. A COMPOUND OF THE FORMULA
 2. The compound of claim 1 wherein
 3. The compound of claim 1 wherein
 4. The compound of claim 1 wherein
 5. The compound of claim 1 wherein 